Novel starlike C-60-bonding polymers were synthesized by using the iniferter technique. The fullerene C-60 with pendent N,N-diethyldithiocarbamate groups (C-60-SR) was used as polyfunctional photoiniferter. The effects of UV-irradiation time and ambient temperature on the molecular weight of polymer were investigated. The photopolymerization with C-60-SR proceeded via a living-radical mechanism, and gave soluble polyfunctional polymers (photoiniferters). Multiple polymer arms were attached to the C-60 core and the polymers obtained by C-60-SR could also be used as excellent crosslinking agents.